CN101274994B - Stabilizing agent compound for koroseal - Google Patents
Stabilizing agent compound for koroseal Download PDFInfo
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- CN101274994B CN101274994B CN2008100874931A CN200810087493A CN101274994B CN 101274994 B CN101274994 B CN 101274994B CN 2008100874931 A CN2008100874931 A CN 2008100874931A CN 200810087493 A CN200810087493 A CN 200810087493A CN 101274994 B CN101274994 B CN 101274994B
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Abstract
The invention provides a stabilizer composition for chloroethylene resin with excellent processing performance and high efficiency of color stabilization and chloroethylene resin composition with excellent color stabilization without generating biological deterioration. The stabilizer composition for chloroethylene resin of the invention is characterized in that the composition is composed of paste or liquid composition containing (A) fatty acid methyl ester with 12 to 30 carbon atoms and 10 to 80 mass% and (B) stearoyl benzoyl methane. The chloroethylene resin composition contains the stabilizer composition.
Description
Technical field
The present invention relates to stabilizing agent compound for koroseal; At length say, relate to the pasty state that contains stearoyl benzoyl methane or aqueous vinyl chloride resin with stabiliser compsn and contain the vinyl chloride resin composition that the shaped material mainly as various resin components etc. of this stabiliser compsn uses.
Background technology
Vinyl chloride-based resin is heating when being shaped processing, is easy to take place the thermolysis that mainly caused by dehydrochlorination, and the deterioration of mechanical properties or the deterioration of color and luster take place, and therefore adds one or more thermo-stabilizers and uses.
As one of this stabilizing agent compound for koroseal composition, use the excellent beta-diketone compound of stabilization of color and luster, and widely-used phenyl phenacyl ketone or stearoyl benzoyl methane (below be called SBM).Particularly, above-mentioned SBM is the excellent stabilizer element of wholesomeness of FDA approval, is used for toy etc.
On the other hand, the viewpoint from the property handled needs pasty state or aqueous stabiliser compsn.As the method for using powder stabilizer element or HV stabilizer element as pasty state or aqueous stabiliser compsn, known have epoxidized vegetable oil or two (2-ethylhexyl) phthalic ester etc. as vinyl chloride resin with stablizer or softening agent and known fraction is engaged in the method in the aforementioned stable agent composition.But, pasty state that so obtains or aqueous stabiliser compsn have when prolonged preservation or during winter mobile deterioration, curing, composition deposition, problem such as be separated.
Particularly, owing to be combined with the tendency that the pasty state stablizer of SBM has viscosity increased,, be necessary to cooperate a large amount of epoxidised soybean oil etc. therefore in order to improve its flowability.For the stablizer that uses dilution like this obtains sufficient stabilization effect, be necessary to cooperate in large quantities stabiliser compsn, so the rerum natura of gained vinyl chloride resin composition reduces.Thereby, when limiting use level, have the problem that can not realize sufficient color and luster stabilization in order to prevent rerum natura from reducing.
Summary of the invention
Therefore, the 1st purpose of the present invention is to provide a kind of property handled excellence, the high stabilizing agent compound for koroseal of while color and luster stabilization effect.
The 2nd purpose of the present invention is to provide the vinyl chloride resin composition that a kind of color stability is excellent, the rerum natura reduction can not take place simultaneously.
The inventor etc. further investigate in order to solve above-mentioned each problem; The result finds through cooperating specific fatty acid methyl ester and a spot of SBM; Can obtain low viscous pasty state or aqueous stabilizing agent compound for koroseal, thereby accomplish the present invention.
Promptly; The present invention is stabilizing agent compound for koroseal and the vinyl chloride resin composition that contains this stabiliser compsn; Said stabilizing agent compound for koroseal is characterised in that, it is that the pasty state or the liquid composition of (B) stearoyl benzoyl methane of 12～30 fatty acid methyl ester and 1～8 quality % constitutes by (A) carbonatoms that contains 10～80 quality %.
Among the present invention, preferably above-mentioned (A) carbonatoms is that the content of 12～30 fatty acid methyl ester is 20～80 quality %.In addition, be 12～30 fatty acid methyl ester as above-mentioned (A) carbonatoms, preferably use the vegetable fatty acids methyl esters, especially preferably use methyl soyate.
Although stabilizing agent compound for koroseal of the present invention contains and has high color and luster and improve the also excellent SBM of effect, wholesomeness; Since be when low temperature (5～10 ℃) have excellent flowability, simultaneously have excellent prolonged preservation property, the curing behind the cryopreservation or be separated etc. through the time change the pasty state that also is able to suppress or aqueous, therefore be suitable for obtaining to make flexibility excellence, the also excellent vinyl chloride resin composition of rerum natura simultaneously.
Embodiment
Following preferred implementation according to the present invention at length describes.
Pasty state of the present invention or aqueous stabilizing agent compound for koroseal be contain 10～80 quality %, more preferably the carbonatoms of 20～80 quality % be the SBM of 12～30 fatty acid methyl ester and 1～8 quality % as must compsn composition, that in liquid, be suspended with fine solid particles, have flowability.
The content of above-mentioned fatty acid methyl ester is during less than 10 quality %, and mobile to improve effect little; Content is during more than 80 quality %, and is excessive to the plasticization effect of vinyl chloride-based resin, so the rerum natura of the vinyl chloride resin composition of gained reduces, or product surface can take place under hot environments such as summer show uncomfortable situation such as binding property.Particularly, contain 20 quality % when above, mobile to improve effect big, is preferred.In addition, the content of above-mentioned stearoyl benzoyl methane is during less than 1 quality %, and the stabilization effect of color and luster is little; Use level is during more than 8 quality %, the mobile reduction, the property handled variation.
As constituting the lipid acid that carbonatoms used in the present invention is 12～30 fatty acid methyl ester, for example can enumerate out saturated or undersaturated lipid acid such as LAURIC ACID 99 MIN, tetradecanoic acid, palmitinic acid, Triple Pressed Stearic Acid, Unimac 5680, ricinolic acid, linolic acid, linolenic acid, oleic acid, eicosanoic acid 、 docosoic, sinapinic acid or as the soya fatty acid of the fatty acid mixt that the hydrolysis natural fats and oils obtained, coco-nut oil fatty acid, tung oil lipid acid, rapeseed oil fatty acid, cottonseed oil fatty acid, animal oil and fat lipid acid, fish oil fatty acid etc.
Among the present invention, as above-mentioned fatty acid methyl ester, the methyl esters of the mobile excellent vegetable fatty acid when preferably using low temperature, the viewpoint of the flowability when obtaining easy property and low temperature is especially preferably used the methyl esters of soya fatty acid.
As other composition that constitutes stabilizing agent compound for koroseal of the present invention; Except to use as the normally used metal of the stablizer of vinyl chloride-based resin at least be stablizer any, can also use is the various additives that stablizer uses with metal usually.
Above-mentioned metal is that for example can to enumerate out lead be stablizer, metal salts of organic acids, organotin stabilizer and their one package stabilizer etc. to stablizer.
As lead is stablizer, for example can enumerate out that the plumbous 、 docosoic of white lead, lead silicate white, sublimed lead, two sublimed leads, tribasic lead sulfate, basic lead sulfite, dibasic lead phosphite, silica gel co-precipitation lead silicate, dibasic lead phthalate, tribasic lead maleate, lead salicylate, lead stearate, alkali formula lead stearate, dibasic lead stearate, lead laurate, lead octoate 36,12-oxystearic acid is plumbous, lead naphthenate etc.
As metal salts of organic acids; Can use metal (Li, Na, K, Mg, Ca, Ba, Sr, Zn, Sn, the Al etc.) salt of carboxylic acid, organophosphorus acids or phenols etc., this carboxylic acid for example can be enumerated out the mixture, phenylformic acid, p-tert-butylbenzoate, ethyl benzoate, isopropyl benzoate, toluylic acid, mesitylenic acid, Whitfield's ointment, Whitfield's ointment uncle 5-monooctyl ester, naphthenic acid, cyclohexane carboxylic of the above-mentioned acid of caproic acid, sad, n-nonanoic acid, 2 ethyl hexanoic acid, capric acid, neodecanoic acid, undecylenic acid, LAURIC ACID 99 MIN, tetradecanoic acid, palmitinic acid, Triple Pressed Stearic Acid, Unimac 5680,12-oxystearic acid, chlorine Triple Pressed Stearic Acid, 12-stearoxylic acid, phenyl stearic acid, ricinolic acid, linolic acid, linolenic acid, oleic acid, eicosanoic acid, docosoic, sinapinic acid, brassidic acid and type acidoid and natural origins such as animal oil and fat lipid acid, coco-nut oil fatty acid, tung oil lipid acid, soya fatty acid, rapeseed oil fatty acid and cottonseed oil fatty acid etc.
In addition, as above-mentioned organophosphorus acids, for example can enumerate out mono phosphoric acid ester or dioctyl ester, mono phosphoric acid ester or two (dodecyl) ester, mono phosphoric acid ester or two (octadecyl) ester, mono phosphoric acid ester or two (nonyl phenyl) ester, phosphonic acids nonyl phenylester, phosphonic acids stearyl ester etc.As above-mentioned phenols, can enumerate out phenol, cresols, ethylphenol, cyclohexylphenol, nonylphenol, dodecyl phenol etc.
These metal salts of organic acids can or be crossed basic complex for normal salt, hydrogen salt, subsalt.
As above-mentioned organotin is stablizer; For example can enumerate out stannic acid methyl esters, stannic acid butyl ester, stannic acid monooctyl ester, dimethyl tin oxide, Dibutyltin oxide, dioctyl tin oxide, dimethyl-sulfuration tin, dibutyltin sulfide, dioctyl tin sulfide, monobutyl oxidation of sulfureted tin, thiostannic acid methyl esters, thiostannic acid butyl ester, thiostannic acid monooctyl ester, dibutyl tin dilaurate, dibutyl distearyl acid tin, dioctyl two oleic acid tin, dibutyl alkali formula tin laurate, dibutyl two Ba Dousuan tin, dibutyl tin two (butoxy Diethylene Glycol malate), dibutyl tin Methyl Octyl NSC 6366 malates, dibutyl tin iso-octyl 1,4-butyleneglycol malate, two (methylacrylic acid) dibutyl tin, dibutyl two styracin tin, dioctyl tin two (oleyl malate), dibutyl tin two (stearyl-malate), dibutyl methylene-succinic acid tin, dioctyl oxysuccinic acid tin, dimethyl-two Ba Dousuan tin, dioctyl tin two (butyl malate), dibutyl dimethanol tin, dibutyl two lauryl alcohol tin, dioctyl terepthaloyl moietie tin, tetramethylolmethane Dibutyltin oxide condenses, two (lauryl mercaptan) tin of dibutyl, two (stearyl-mercaptan) tin of dimethyl-, monobutyl three (lauryl mercaptan) tin, dibutyl β-Qiu Jibingsuan tin, dioctyl β-Qiu Jibingsuan tin, dibutyl Thiovanic acid tin, Monobutyltin three (iso-octyl mercaptoacetate), single tin octylate three (2-ethylhexyl mercaptoacetate), dibutyl tin two (iso-octyl mercaptoacetate), dioctyl tin two (iso-octyl mercaptoacetate), dioctyl tin two (2-ethylhexyl mercaptoacetate), tin methide two (iso-octyl mercaptoacetate), tin methide two (iso-octyl mercaptopropionic acid ester), Monobutyltins three (iso-octyl mercaptopropionic acid ester), two [monobutyl two (different carbonyl octyloxy sulfonium methylide) tin] sulfide, two [dibutyl list (different carbonyl octyloxy sulfonium methylide) tin] sulfide, monobutyl monochloro tin two (iso-octyl mercaptopropionic acid ester), monobutyl monochloro tin two (iso-octyl mercaptoacetate), two (lauryl mercaptan) tin of monobutyl monochloro, butyl tin two (ethyl cellosolve malate), two (dioctyl tin butyl malate) malates, two (methyl tin diisooctyl mercaptoacetate) disulphide, two (methyl/tin methide list/diisooctyl mercaptoacetate) disulphide, two (methyl tin diisooctyl mercaptoacetate) trisulphide, two (butyl tin diisooctyl mercaptoacetate) trisulphide, 2-butoxy carbonyl ethyl tin three (butyl mercaptoacetate) etc.
Above-mentioned metal is that the content of stablizer is preferably 20～50 quality % in the stabilizing agent compound for koroseal of the present invention, 30～40 quality % more preferably.
In stabilizing agent compound for koroseal of the present invention, can in the scope of not damaging effect of the present invention, suitably use the softening agent that is generally used in the vinyl chloride-based resin.It is softening agent that above-mentioned softening agent for example can be enumerated out phthalic esters such as Witcizer 300, the own ester of O-phthalic acid butyl, diheptyl phthalate, DOP, DINP, Di Iso Decyl Phthalate, dilauryl phthalate, dicyclohexyl phthalate, dioctyl terephthalate; Adipic acid esters such as Octyl adipate, diisononyl adipate, diisodecyl adipate, hexanodioic acid two (butyldiglycol) ester are softening agent; SULPHOSUCCINIC ACID ESTERs such as triphenylphosphate, Tritolyl Phosphate, tricresyl phosphate (YLENE) ester, tricresyl phosphate (isopropyl phenyl) ester, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tricresyl phosphate (butoxyethyl group) ester, octyl phosphate diphenyl ester are softening agent; Make spent glycol, Diethylene Glycol, triethylene glycol, 1 as polyvalent alcohol; 2-Ucar 35,1; Ammediol, 1,3 butylene glycol, 1,4-butyleneglycol, 1; 5-pinakon, 1; 6-pinakon, NSC 6366 etc. use oxalic acid, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, phthalic acid, m-phthalic acid, terephthalic acid etc. as diprotic acid, and the polyester that uses monohydroxy-alcohol, monocarboxylic acid to obtain as stopper as required are a softening agent; Other also has tetrahydrophthalic acid is that softening agent, nonane diacid are that softening agent, sebacic acid are that softening agent, Triple Pressed Stearic Acid are that softening agent, Hydrocerol A are that softening agent, trimellitic acid are that softening agent, pyromellitic acid are that softening agent, biphenylene polycarboxylic acid are softening agent etc.Content when adding above-mentioned softening agent is preferably 20～80 quality % in the vinyl chloride resin composition of the present invention, 30～50 quality % more preferably.
In addition; In stabilizing agent compound for koroseal of the present invention; Can also in the scope of not damaging effect of the present invention, add as the normally used various additives of koroseal additive, for example organophosphorus compounds, phenol system or sulphur are that inhibitor, hydrotalcite compound, epoxy compounds, polyol compound, beta-diketone compound, UV light absorber, hindered amine are photostabilizer, weighting agent etc.
As above-mentioned organophosphorus compounds; For example can enumerate out triphenylphosphate, tricresyl phosphate (2; The 4-di-tert-butyl-phenyl) ester, tricresyl phosphate (nonyl phenyl) ester, tricresyl phosphate (dinonyl phenyl) ester, tricresyl phosphate (single, two mixing nonyl phenyl) ester, phenylbenzene phosphate ester acid, 2; 2 '-methylene-bis (4; The 6-di-tert-butyl-phenyl) octyl phosphate, phenylbenzene decyl SULPHOSUCCINIC ACID ESTER, phenyl diiso decyl SULPHOSUCCINIC ACID ESTER, tributyl phosphate, three (2-ethylhexyl) SULPHOSUCCINIC ACID ESTER, tridecyl phosphate, tricresyl phosphate lauryl, dibutyl phosphate ester acid, dilauryl phosphate ester acid, three lauryl phosphorotrithioates, two (NSC 6366) 1,4-hexanaphthene dimethyl-bisphosphate, two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphate, two (2; 6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphate, distearyl acyl group pentaerythritol diphosphate, phenyl-4; 4 '-isopropylidene biphenol pentaerythritol diphosphate, four (C12～C15 mixed alkyl)-4,4 '-isopropylidene phenylbenzene bisphosphate, hydrogenation-4,4 '-isopropylidene biphenol polyphosphate, two (octyl phenyl) two [4; 4 '-positive butylidene two (the 2-tertiary butyl-5-methylphenol)] 1; 6-pinakon bisphosphate, four (tridecyls) 4, two (the 2-tertiary butyl-5-methylphenol) bisphosphates, six (tridecyl) 1,1 of 4 '-butylidene; 3-three (2-methyl-5-tert-butyl-hydroxy phenyl) butane triguaiacyl phosphate, 9; 10-dihydro-9-oxy generation-10-phospho hetero phenanthrene-10-oxide compound, 2-butyl-2-ethyl glycol 2,4,6-tri-butyl-phenol phosplate etc.Content when adding above-mentioned organophosphorus compounds is preferably 5～70 quality % in the stabilizing agent compound for koroseal of the present invention, 10～50 quality % more preferably.
As above-mentioned phenol is inhibitor, for example can enumerate out 2,6-di-t-butyl-p-cresol, 2,6-phenylbenzene-4-octadecane oxygen base phenol, stearyl-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic ester, distearyl acyl group (3, the 5-di-tert-butyl-4-hydroxyl benzyl) phosphonic acid ester, sulfo-di ethylene bis [(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], 4,4 '-thiobis (the 6-tertiary butyl-meta-cresol), 2-octylsulfo-4; 6-two (3,5-di-t-butyl-4-hydroxyphenoxy)-s-triazine, 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol), two [3; Two (4-hydroxyl-3-tert-butyl-phenyl) butyric acid of 3-] diol ester, 4,4 '-butylidene two (the 6-tertiary butyl-meta-cresol), 2,2 '-ethylenebis (4; The 6-DI-tert-butylphenol compounds), 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl] butane, two [the 2-tertiary butyl-4-methyl-6-(the 2-hydroxyl-3-tertiary butyl-5-methyl-benzyl) phenyl] terephthalate, 1; 3,5-three (2,6-dimethyl--3-hydroxyl-4-tertiary butyl benzyl) isocyanuric acid ester, 1; 3,5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid ester, 1; 3,5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl)-2; 4,6-Three methyl Benzene, 1,3; 5-three [(3, the 5-di-tert-butyl-hydroxy phenyl) propionyloxy ethyl] isocyanuric acid ester, four [methylene radical-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] methane, the 2-tertiary butyl-4-methyl-6-(the 2-acryloxy-3-tertiary butyl-5-methyl-benzyl) phenol, 3; Two [1,1-dimethyl--2-hydroxyethyl]-2,4 of 9-; 8,10-four oxaspiros [5,5] undecane-two [β-(3-tertiary butyl-4-hydroxy-5-butyl phenyl) propionic ester], triethylene glycol two [β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester] etc.
Content when adding above-mentioned phenol and being inhibitor is preferably 1～20 quality % in the stabilizing agent compound for koroseal of the present invention, 5～10 quality % more preferably.
As above-mentioned sulphur is inhibitor, for example can enumerate out the dialkyl group thiodipropionate class such as two lauryls, two myristins, myristin stearate, SUNSOFT Q-182S of thio-2 acid and β-alkyl thiol propionic acid ester of tetramethylolmethane four polyvalent alcohols such as (β-dodecyl mercaptopropionic acid ester) etc.
Content when adding above-mentioned sulphur and being inhibitor is preferably 1～20 quality % in the stabilizing agent compound for koroseal of the present invention, 5～10 quality % more preferably.
The compound salt that above-mentioned hydrotalcite compound preferably uses magnesium shown in the formula (I) and aluminium or zinc, magnesium and aluminium to constitute.These materials can also be with the product after the crystal water dehydration.
Mg
X1Zn
X2Al
2·(OH)
2(X1+X2)+4·(CO
3)
1-y/2(ClO
4)
y·mH
2O (I)
X1 in the formula, x2 and y represent to satisfy the numerical value of condition shown in the following formula respectively, and m representes 0 or integer arbitrarily.0≤x2/x1＜10、2≤(x1+x2)＜20、0≤y≤2。
Above-mentioned hydrotalcite compound can be that natural goods can also be a synthetics.The compound method of this synthetics can be enumerated out the known method of being put down in writing in the special public clear 46-2280 communique of Japan, the special public clear 50-30039 communique of Japan, the special public clear 51-29129 communique of Japan, the special fair 3-36839 communique of Japan and the japanese kokai publication sho 61-174270 communique etc.In addition, among the present invention, the crystalline structure of above-mentioned hydrotalcite compound, crystal particle diameter etc. can use ad lib.
In addition; As above-mentioned hydrotalcite compound, its back, surface use can also covered with metal organic sulfonate, high fatty acid amide, high-grade aliphatic ester or paraffin such as higher fatty acid metal-salts such as higher fatty acid such as Triple Pressed Stearic Acid, oleic acid an alkali metal salt, Witco 1298 Soft Acid an alkali metal salt etc.
The content of above-mentioned hydrotalcite compound is preferably 1～20 quality % in the stabilizing agent compound for koroseal of the present invention, 1～10 quality % more preferably.When the amount of hydrotalcite compound surpasses 20 quality %,, therefore not preferred in the possibility that prolonged preservation happens occasionally and is separated.
Above-mentioned epoxy compounds for example can be enumerated out epoxidised soybean oil, epoxidation linseed oil, epoxidation tung oil, epoxidation fish oil, epoxidation tallow oil, epoxidation Viscotrol C, epoxidation safflower wet goods epoxidation vegetable and animals oils; Epoxidation methyl stearate, epoxidation butyl stearate, epoxidation Triple Pressed Stearic Acid 2-ethylhexyl, epoxidation Triple Pressed Stearic Acid stearyl ester, epoxidized polybutadiene, three (epoxidation propyl group) isocyanuric acid ester, epoxidation ready denier oil acid ester, epoxidation linseed oil fatty ester, bisphenol A diglycidyl ether, VCH diepoxide, two tetrahydrobenzene diepoxides, 3, epoxy compoundss such as 4-epoxycyclohexyl methyl epoxycyclohexane carboxylate etc.
Content when adding above-mentioned epoxy compounds is preferably 0.5～20 quality % in the vinyl chloride resin composition of the present invention, 1～10 quality % more preferably.
Above-mentioned polyol compound for example can be enumerated out the Triple Pressed Stearic Acid half ester of TriMethylolPropane(TMP), two (trishydroxymethyl) propane, tetramethylolmethane, Dipentaerythritol, polypentaerythritol, tetramethylolmethane or Dipentaerythritol, two (Dipentaerythritol) adipic acid ester, glycerine, three (2-hydroxyethyl) isocyanuric acid ester etc.
Content when adding above-mentioned polyol compound is preferably 1～50 quality % in the stabilizing agent compound for koroseal of the present invention, 5～30 quality % more preferably.
Above-mentioned beta-diketone compound for example can be enumerated out methyl ethyl diketone, triacetyl methane, 2; 4; 6-triketone in heptan, butyryl radicals ethanoyl methane, lauroyl ethanoyl methane, palmitoyl ethanoyl methane, stearyl-ethanoyl methane, phenyl acetyl ethanoyl methane, dicyclohexyl carbonyl methane, benzoyl-formyl radical methane, benzoyl-ethanoyl methane, phenyl phenacyl ketone, octyl group benzoyl-methane, two (4-octyl group benzoyl-) methane, benzoyl-diacetyl methane, 4-anisoyl benzoyl-methane, two (4-ethyloic benzoyl-) methane, 2-ethyloic benzoyl-ethanoyl octyl group methane, dehydro-acetic acid, hexanaphthene-1; 3-diketone, 3; 6-dimethyl--2,4-dioxy hexanaphthene-1-carboxylate methyl ester, 2-acetyl cyclohexanone, methone, 2-2-benzoyl-cyclohexane etc.
Among the present invention, also can use the metal-salt of these beta-diketone compounds.As the metal species that this Beta-diketone metal salt can be provided, for example can enumerate out basic metal such as lithium, sodium and potassium; Alkaline-earth metals such as magnesium, calcium, strontium and barium; Zinc, aluminium, tin, tin alkyl etc.
Content when adding above-mentioned beta-diketone compound is preferably 0.5～10 quality % in the stabilizing agent compound for koroseal of the present invention, 1～5 quality % more preferably.
Above-mentioned UV light absorber for example can be enumerated out 2,4 dihydroxyl benzophenone, 2-hydroxyl-4-methoxy benzophenone, 2-hydroxyl-4-octyloxy UVNUL MS-40,5,5 '-methylene-bis 2-hydroxy benzophenone ketones such as (2-hydroxyls-4-methoxy benzophenone); 2-(2-hydroxy-5-methyl base phenyl) benzotriazole, 2-(2-hydroxyl-uncle's 5-octyl phenyl) benzotriazole, 2-(2-hydroxyl-3; The 5-di-tert-butyl-phenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3-t-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxyl-3; The 5-dicumylphenyl) benzotriazole, 2,2-(2-hydroxy phenyl) benzotriazole category of the macrogol ester of 2 '-methylene-bis (uncle's 4-octyl group-6-benzotriazole base) phenol, 2-(the 2-hydroxyl-3-tertiary butyl-5-carboxyphenyl) benzotriazole etc.; Salol, resorcinol monobenzoate, 2,4-di-tert-butyl-phenyl-3,5-di-tert-butyl-4-hydroxybenzoic acid ester, hexadecyl-3, benzoates such as 5-di-tert-butyl-4-hydroxybenzoic acid ester; 2-ethyl-2 '-oxyethyl group oxanilide, 2-oxyethyl group-4 '-dodecyl oxanilide etc. replace the oxanilide class; Ethyl-alpha-cyano-β, β-diphenylacrylate ester, methyl-2-cyanic acid-cyanoacrylates such as 3-methyl-3-(p-methoxyphenyl) propenoate etc.
Content when adding above-mentioned UV light absorber is preferably 0.5～10 quality % in the stabilizing agent compound for koroseal of the present invention, 1～5 quality % more preferably.
Above-mentioned hindered amine is that photostabilizer for example can enumerate out 2,2,6,6-tetramethyl--4-piperidyl stearate, 1,2,2,6,6-pentamethyl--4-piperidyl stearate, 2; 2,6,6-tetramethyl--4-piperidyl benzoic ether, two (2,2,6,6-tetramethyl--4-piperidyl) sebate, two (1,2,2; 6,6-pentamethyl--4-piperidyl) sebate, four (2,2,6,6-tetramethyl--4-piperidyl) butane tetracarboxylic acid esters, four (1,2,2,6; 6-pentamethyl--4-piperidyl) butane tetracarboxylic acid esters, two (1,2,2,6,6-pentamethyl--4-piperidyl) two (tridecyl)-1,2,3,4-butane tetracarboxylic acid esters, two (1; 2,2,6,6-pentamethyl--4-piperidyl)-2-butyl-2-(3, the 5-di-tert-butyl-4-hydroxyl benzyl) malonic ester, 1-(2-hydroxyethyl)-2,2,6; 6-tetramethyl--4-piperidines alcohol/ethyl succinate polycondensate, 1, two (2,2,6, the 6-tetraethyl--4-piperidyl amino) hexanes/ethylene dibromide polycondensate, 1 of 6-, 6-two (2,2; 6,6-tetramethyl--4-piperidyl amino) hexane/2,4-two chloro-6-morpholinoes-s-triazine polycondensate, 1, two (2,2,6,6-tetramethyl--4-piperidyl amino) hexane/2 of 6-; 4-two chloro-uncle 6-octyl group amino-s-triazine polycondensates, 1,5,8, [2,4-is two, and (N-butyl-N-(2,2,6 for 12-four; 6-tetramethyl--4-piperidyl) amino)-and s-triazine-6-yl]-1,5,8,12-four aza-dodecanes, 1,5,8,12-four [2; Two (N-butyl-N-(1,2,2,6,6-pentamethyl--4-piperidyl) amino)-s-triazine-6-yls of 4-]-1,5,8; 12-four aza-dodecanes, 1,6,11-three [2, two (N-butyl-N-(2,2,6,6-tetramethyl--4-piperidyl) amino)-s-triazines of 4--6-base is amino] undecane, 1; 6, hindered amine compounds such as 11-three [2, two (N-butyl-N-(1,2,2,6,6-pentamethyl--4-piperidyl) amino)-s-triazines of 4--6-base is amino] undecane.Content when adding above-mentioned hindered amine and being photostabilizer is preferably 0.5～10 quality % in the stabilizing agent compound for koroseal of the present invention, 1～5 quality % more preferably.
As the object lesson of above-mentioned weighting agent, can enumerate out metal silicate such as lime carbonate, quicklime, calcium hydroxide, zinc oxide, zinc hydroxide, zinc carbonate, zinc sulphide, Natural manganese dioxide, Marinco H, magnesiumcarbonate, aluminum oxide, white lake, sodium aluminium silicate, hydrotalcite, hydrocalumite, pure aluminium silicate, Magnesium Silicate q-agent, Calucium Silicate powder, zeolite, atlapulgite, talcum, clay, colcother, asbestos, ANTIMONY TRIOXIDE SB 203 99.8 PCT etc.
Content when adding above-mentioned weighting agent is preferably 5～50 quality % in the stabilizing agent compound for koroseal of the present invention, 10～30 quality % more preferably.
In addition, in the stabilizing agent compound for koroseal of the present invention, can in the scope of not damaging effect of the present invention, be added on normally used stabilizing additive in the vinyl chloride-based resin.This stabilizing additive for example can be enumerated out diphenyl thiourea, aniline two sulphur triazines, melamine, phenylformic acid, styracin, p-tert-butylbenzoate, zeolite, perchlorate etc.
In addition; In stabilizing agent compound for koroseal of the present invention; Can also in the scope of not damaging effect of the present invention, be added on normally used additive in the vinyl chloride-based resin as required, for example linking agent, antistatic agent, anti-clouding agent, anti-precipitation agent, surface treatment agent, lubricant, fire retardant, fluorescent agent, mould inhibitor, disinfectant, whipping agent, metal inert agents, releasing agent, pigment, processing aid, inhibitor, photostabilizer etc.
In addition, stabilizing agent compound for koroseal of the present invention can irrespectively use with the working method of vinyl chloride-based resin, for example can be fit to be used in Roller Machining, extrusion moulding processing, fusion casting method, extrusion forming processing etc.
Stabilizing agent compound for koroseal of the present invention when low temperature (5～10 ℃) mobile and under low-temperature condition the good fluidity after the prolonged preservation, can not solidify or be separated.Certainly, even if under the condition of high temperature after the prolonged preservation, do not solidify yet or be separated.
The vinyl chloride resin composition of the present invention that is added with stabilizing agent compound for koroseal of the present invention for example can be used for material of construction such as wall material, bed material, window frame, wallpaper; Wire covering materials; Automobile is used inside/outside decorative material; Material is used with agricultural in house, tunnel etc.; Packaging material for food such as preservative film, plate; Groceries or daily necessities such as coating, flexible pipe, conduit, sheet material, toy; In the various uses such as sanitary material.Stabilizing agent compound for koroseal particularly of the present invention can be suitable in food, sanitary use or toy, the daily necessities etc. when using nontoxic VT 18.
Below further specify the present invention through embodiment, but the present invention is not limited to these embodiment.
In addition, pasty vinyl chloride of the present invention is shown is resin to embodiment with the preparation and their evaluation of stabiliser compsn and the preparation and their evaluation that contain the vinyl chloride resin composition of this stabilizing agent compound for koroseal; Preparation and evaluation thereof that comparative example illustrates the preparation and the evaluation thereof of comparison stabilizing agent compound for koroseal and contains the comparison vinyl chloride resin composition of this comparison stabilizing agent compound for koroseal.In addition, " part " among the embodiment or " % " are based on quality criteria.
[embodiment 1～3, comparative example 1]
Preparing pasty vinyl chloride of the present invention with the proportioning shown in the table 1 is that resin is with stabiliser compsn and comparison stabilizing agent compound for koroseal.
For the stabiliser compsn of gained, the viscosity under measuring 25 ℃ is estimated mobilely, and the result is shown in Table 1.
In addition, mix as follows and prepare the vinyl chloride resin composition that contains aforementioned stable agent compsn.
< cooperation >
Vinyl chloride resin (polymerization degree 700) 100 mass parts
DOP 40 mass parts
Epoxidised soybean oil 3 mass parts
Stabiliser compsn (table 1; The cooperation benchmark of table 1 is a mass parts) 1.5 mass parts
This vinyl chloride resin composition is carried out rolling processing under 170 ℃, make the thick sheet material of 0.7mm.This sheet material put into the melanism time of measuring in 190 ℃ the gill baking oven (minute).In addition, the above-mentioned sheet material that 0.7mm is thick sticks together and 180 ℃ of processing 5 minutes or 30 minutes of pressurizeing down, makes the thick sheet material of 2mm respectively.For these sheet materials of gained, measure yellow chromaticity (Y.I) as the pressurization tint permanence.In order to make the powder components in proportions in the stabiliser compsn consistent, making Ca/Zn is that the total amount of powder stablizer and SBM is certain, is 43.2 quality % of stabiliser compsn.The result is shown in Table 1.
Table 1
The situation of embodiment 1,2,3 is, because viscosity is below 25000, therefore can be used as to stick with paste and handle, and the situation of comparative example 1,2 is that because viscosity surpasses 30000, therefore lack of fluidity can not be handled as the stablizer of pasty state.Hence one can see that, through cooperating specific fatty acid methyl ester of the present invention as aqueous composition, can obtain mobile excellent pasty state stablizer.In addition; Comparison by embodiment 2 and comparative example 3 can be known, even if the aqueous composition stabiliser compsn identical with situation of the present invention, when the use level of SBM increases; Flowability also can sharply reduce; At this moment, the melanism time under 190 ℃ of resin combination is short, and the painted evaluation of pressurizeing is also than the present invention difference.And, can know that by the comparison of embodiment 1 and comparative example 4 when the usage quantity of SBM was very few, painted evaluation reduced.Can know by these embodiment and comparative example; Only when using SBM with the use level of specified range of the present invention and cooperating a certain amount of specific fatty acid methyl ester, the pasty vinyl chloride that could obtain to have excellent flowability and painted improved effect is that resin is used stabiliser compsn.
In addition, therefore low-molecular weight compounds such as methyl propionate need not compare experiment especially owing to becoming gas in the time volatilization of the heat processed of resin, only will be as the aqueous composition of pasty state stabiliser compsn and general epoxidised soybean oil as comparison other.
Stabilizing agent compound for koroseal of the present invention be have high color and luster when improving effect, low temperature (5～10 ℃) have excellent flowability, simultaneously have excellent prolonged preservation property, the curing behind the cryopreservation or be separated etc. through the time change the pasty state that also is able to suppress or aqueous, therefore be suitable for obtaining to make flexibility excellence, the also excellent vinyl chloride resin composition of rerum natura simultaneously.
Claims (5)
1. stabilizing agent compound for koroseal; It is characterized in that; It is made up of pasty state or liquid composition, and (A) carbonatoms that said pasty state or liquid composition contain 10～80 quality % is 12～30 fatty acid methyl ester and (B) stearoyl benzoyl methane of 1～8 quality %.
2. stabilizing agent compound for koroseal according to claim 1, wherein, said (A) carbonatoms is that the content of 12～30 fatty acid methyl ester is 20～80 quality %.
3. stabilizing agent compound for koroseal according to claim 1 and 2, wherein, said (A) carbonatoms is that 12～30 fatty acid methyl ester is the vegetable fatty acids methyl esters.
4. stabilizing agent compound for koroseal according to claim 3, wherein, said vegetable fatty acids methyl esters is a methyl soyate.
5. a vinyl chloride resin composition is characterized in that, it contains each described stabilizing agent compound for koroseal of claim 1～4.
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| Application Number | Priority Date | Filing Date | Title |
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| JP083982/2007 | 2007-03-28 | ||
| JP2007083982A JP5116141B2 (en) | 2007-03-28 | 2007-03-28 | Stabilizer composition for vinyl chloride resin |
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| CN101274994B true CN101274994B (en) | 2012-06-27 |
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| CN102791788B (en) * | 2009-09-30 | 2014-09-24 | 陶氏环球技术有限责任公司 | Heat stabilized polymeric composition with epoxidized fatty acid ester plasticizer |
| CN102153824B (en) * | 2011-04-20 | 2012-11-21 | 山东慧科助剂股份有限公司 | Environmental-friendly high-efficiency composite heat stabilizer for tribasic zinc PVC (polyvinyl chloride) and preparation method of environmental-friendly high-efficiency composite heat stabilizer |
| EP2857458B1 (en) * | 2012-05-24 | 2017-01-04 | Adeka Corporation | Stabilizer composition, resin composition, and molded product using same |
| CN105218972A (en) * | 2015-10-13 | 2016-01-06 | 云南锡业股份有限公司 | A kind of polyvinyl chloride card specific complex thermo-stabilizer and preparation method thereof |
| CN106543476B (en) * | 2016-12-08 | 2019-01-04 | 肇庆学院 | A kind of composite material and preparation method for PVC heat stabilizer |
| JP2020147694A (en) * | 2019-03-14 | 2020-09-17 | 田島ルーフィング株式会社 | Resin composition for floor material and floor material |
| CN110802853A (en) * | 2019-10-17 | 2020-02-18 | 江苏升茂塑胶制品有限公司 | Method for producing door plate based on PVC plastic floor |
| CN112457523A (en) * | 2020-12-18 | 2021-03-09 | 威海市正旺塑业有限公司 | High-stability and high-plasticity composite PVC (polyvinyl chloride) processing aid and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1205722A (en) * | 1995-08-04 | 1999-01-20 | 福尔博国际股份有限公司 | Polymer product manufacture |
| CN1205723A (en) * | 1995-12-21 | 1999-01-20 | 纳幕尔杜邦公司 | Fluorinated ester melt additives for thermoplastic fibers |
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| JPH0559238A (en) * | 1991-08-22 | 1993-03-09 | Witco Corp | Polyvinyl chloride composition and stabilizer therefor |
| JPH1160746A (en) * | 1997-08-28 | 1999-03-05 | Dainippon Ink & Chem Inc | Vinyl chloride-based resin composition and its molded product |
| KR101279230B1 (en) * | 2004-09-29 | 2013-06-26 | 카네카 코포레이션 | Polyvinyl chloride fiber reduced in initial coloration |
| FR2879610B1 (en) * | 2004-12-20 | 2007-06-15 | Rhodia Chimie Sa | STABILIZATION INGREDIENT OF HALOGEN POLYMERS COMPRISING A BETA-DICARBONYL COMPOUND |
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| CN1205722A (en) * | 1995-08-04 | 1999-01-20 | 福尔博国际股份有限公司 | Polymer product manufacture |
| CN1205723A (en) * | 1995-12-21 | 1999-01-20 | 纳幕尔杜邦公司 | Fluorinated ester melt additives for thermoplastic fibers |
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| CN101274994A (en) | 2008-10-01 |
| JP2008239849A (en) | 2008-10-09 |
| TWI460191B (en) | 2014-11-11 |
| JP5116141B2 (en) | 2013-01-09 |
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